The synthesis of ethyne-linked porphyrin nanorings has been achieved by template-directed Sonogashira coupling. The cyclic hexamer and octamer are predicted by density functional theory to adopt low symmetry conformations, due to dihedral twists between neighboring porphyrin units, but their symmetries are effectively D and D, respectively, in solution by H NMR. The fluorescence spectra indicate that the singlet excited states of these nanorings are highly delocalized.
Download full-text PDF |
Source |
|---|---|
| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC5719470 | PMC |
| http://dx.doi.org/10.1021/jacs.7b10710 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Highly Strained, Fully π-Conjugated Porphyrin Cyclophanes: Template-free Synthesis and Global Aromaticity.
Angew Chem Int Ed Engl
October 2024
Department of Chemistry, National University of Singapore, 3 Science Drive 3, 117543, Singapore.
Article Synopsis
- The study focuses on creating porphyrin-based nanohoops, rings, and cages, which are difficult to synthesize but have desirable properties.
- The authors describe a template-free method to synthesize a unique bithiophene-bridged porphyrin cyclophane, revealing its strained structure and electronic characteristics through X-ray analysis.
- The resulting compounds exhibit interesting aromatic properties and reactivity, with the dication being globally aromatic and able to relieve strain through nucleophilic addition with chloride.
Encapsulation of an Au Nanocluster inside a Porphyrin Nanoring Enhances Singlet Oxygen Generation and Photo-Electrocatalytic CO Reduction.
Angew Chem Int Ed Engl
January 2025
Department of Physical Chemistry, University of Geneva, 30 Quai Ernest-Ansermet,1211, Geneva 4, Switzerland.
Article Synopsis
- The study focuses on creating enhanced host-guest complexes using a gold nanocluster and a zinc porphyrin nanoring, which is important in supramolecular chemistry.
- Strong binding was observed between the gold nanocluster and the six-unit zinc porphyrin nanoring, confirmed through various analytical techniques including UV/Vis absorption and mass spectrometry.
- The resulting complex not only stabilizes the gold nanocluster but also shows improved activity and selectivity in photochemical reactions, specifically converting carbon monoxide and generating singlet oxygen.
Polymorphism and flexibility of six-porphyrin nanorings in the solid state.
Chem Sci
September 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory Oxford OX1 3TA UK
Butadiyne-linked porphyrin nanorings are fascinating nanometer-sized platforms for exploring electronic delocalization and aromaticity, and they mimic ultra-fast photosynthetic energy-transfer phenomena in plants and purple bacteria. However, little is known about how they interact in the solid state. Here, we compare the crystal structures of several pseudopolymorphs of a six-porphyrin nanoring template complex, and report the structure of the free-base nanoring co-crystallized with C.
View Article and Find Full Text PDFBimolecular Sandwich Aggregates of Porphyrin Nanorings.
J Am Chem Soc
September 2024
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Oxford, OX1 3TA, U.K.
Extended π-systems often form supramolecular aggregates, drastically changing their optical and electronic properties. However, aggregation processes can be difficult to characterize or predict. Here, we show that butadiyne-linked 8- and 12-porphyrin nanorings form stable and well-defined bimolecular aggregates with remarkably sharp NMR spectra, despite their dynamic structures and high molecular weights (12.
View Article and Find Full Text PDFInsight into magnetically induced ring currents and photophysics of six-porphyrin nanorings.
Phys Chem Chem Phys
August 2024
Department of Optics and Spectroscopy, Tomsk State University, Tomsk, 634050, Russia.
The series of nanorings based on Zn-porphyrins and tetraoxa-isophlorins in different oxidation states ( = 0, 2+, 4+, 6+) have been studied studied computationally at density functional theory level (DFT) using BHandHLYP functional combined with def2-SVP basis sets. Magnetically induced ring currents of nanorings have been calculated using the GIMIC method and the Ampère-Maxwell integration scheme. Ring current calculations show that neutral nanorings sustain equal diatropic and paratropic currents of 8 nA T, resulting in zero net ring current strengths.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!